Improvement of boundary lubrication properties of diamond-like carbon (DLC) films due to metal addition

The effects of added materials such as metals like titanium (Ti), molybdenum (Mo) and iron (Fe) diamond-like carbon (DLC) films on boundary lubrication and microtribological properties were investigated. The nanoindentation hardness and microwear resistance can be improved by adding the proper metal to DLC films, as evaluated by atomic force microscopy (AFM). Boundary lubrication properties of DLC films with metals are improved as comparing with DLC films without metal under lubricant with both MoDTC and ZDDP additives. Moreover, lower friction coefficient of μ=0.03 than carburized steel is exhibited with the appropriate quantity of Ti added. The tribochemical reactant was formed on the sliding surface of the Ti-containing DLC film like as carburized steel. Higher mechanical damping materials containing elements, such as Mo, Zn, P and S, formed tribochemical reactors as observed by X-ray photoemission spectroscopy (XPS) and AFM force modulation methods.     

Topographic and phase-contrast imaging in atomic force microscopy

Phase-contrast imaging in the tapping mode atomic force microscopy (AFM) is a powerful method in surface characterization. This method can provide fine details about rough surfaces, which are normally obscured in topographic imaging. To illustrate some of the capabilities of phase-contrast imaging, AFM studies of Pt/Ti/SiO2/Si and Pb(Zr0.52Ti0.48)O3 (PZT) films were carried out. Phase-contrast imaging revealed fine details of their microstructures, including grain boundaries, triple junctions and twinning, which could not be detected by topographic imaging. The studies showed that phase-contrast imaging is capable of providing superior information about surface characteristics when compared to the standard topographic imaging.     

Characterization of polymer thin films by phase-sensitive acoustic microscopy and atomic force microscopy: a comparative review

The potential of phase-sensitive acoustic microscopy (PSAM) for characterizing polymer thin films is reviewed in comparison to atomic force microscopy (AFM). This comparison is based on results from three-dimensional vector contrast imaging and multimodal imaging using PSAM and AFM, respectively. The similarities and differences between the information that can be derived from the AFM topography and phase images, and the PSAM phase and amplitude micrographs are examined. In particular, the significance of the PSAM phase information for qualitative and quantitative characterization of the polymer films is examined for systems that generate surface waves, and those that do not. The relative merits, limitations and outlook of both techniques, individually, and as a complementary pair, are discussed.     

Topography and nanomechanical properties of tribochemical films derived from zinc dialkyl and diaryl dithiophosphates

In this paper we present recent results from an on‐going effort to characterize the nanomechanical properties of a variety of tribochemical, antiwear films through the use of modern scanning probe techniques. The two types of antiwear wear films studied, derived from zinc dialkyl dithiophosphate (alkyl ZDDP) and zinc diaryl dithiophosphate (aryl ZDDP), were chosen because they possess significantly different wear characteristics. High resolution AFM topographic images showed significant differences between the two types of films. More interestingly, high resolution imaging and quantitative mechanical properties testing using the interfacial force microscope (IFM), revealed different elastic and plastic properties between the two types of films; in addition each type of film possessed several distinct regions with respect to mechanical properties. The maximum values for elastic modulus and hardness were located on the highly loaded regions of the alkyl ZDDP films which exhibited the best tribological performance. In contrast, the aryl ZDDP films, which exhibited poorer antiwear behaviour, were devoid of such resilient regions. Our results correlate the macroscopic wear behavior of the tribochemical films to differences in the mechanical properties on a nanometer scale. This revised version was published online in July 2006 with corrections to the Cover Date.     

Macro and microtribological studies of CrO2 video tapes

Atomic force microscopy (AFM) and its modification-friction force microscopy (FFM) are becoming increasingly important in the understanding of friction, wear, lubrication and nanomechanical property measurements. We describe modified AFM and FFM techniques and present data on microtribological studies of two CrO₂ video tapes. Macro-scale friction measurements were also made on the two tapes. We have observed that macro-scale friction is higher than that on micro-scale. Lower values of micro-scale friction as compared to macro-scale friction may be because of less ploughing contribution in micro-scale friction measurements. The directionality effects observed in micro-scale friction may come from the asymmetrical transfer of wipe material or from the calendering. Differences in the macro-scale friction in the two tapes appear to correlate with the changes in scratch resistance, wear resistance and the hardness of the tape surface on a micro-scale to nano-scales. It is demonstrated that AFM/FFM techniques are valuable in the fundamental understanding of tribology of magnetic tapes.     

Microtribological Properties of Two-Phase Al2O3 Ceramic Studied by AFM and FFM in Air of Different Relative Humidity

Commercially available, monolithic alumina ceramic was modified using CO₂-laser irradiation by surface remelting and adding HfO₂ powder. Scanning electron microscopy revealed that the microstructure of the modified ceramic consisted of a fine lamellar eutectic Al₂O₃–HfO₂ phase embedded in the Al₂O₃ matrix. Differences in the microtribological properties of the matrix and the eutectic phase could be measured by friction force microscopy (FFM) during unlubricated sliding contact with a silicon tip at room temperature as a function of relative humidity of the surrounding air and normal load. The dependence of the friction coefficient and the pull-off force on humidity was explained by the formation of lubricating tribochemical surface layers and described by theoretical models.     

Atomic force microscopy characterization of the chemical contrast of nanoscale patterns fabricated by electron beam lithography on polyethylene glycol oxide thin films

The present paper shows that atomic force microscopy (AFM) imaging of friction force and phase lag in ambient air can be used to characterize the chemical contrast induced by electron beam (EB) irradiation on polyethylene glycol oxide (PEO) surface. Time-of-flight secondary emission mass spectroscopy measurements showed that the EB irradiation generates chemical contrast on PEO surface by decreasing the ether bond density. The AFM measurements showed smaller phase lag and lower friction and adhesive forces on the EB irradiated PEO surface, as compared to the non-irradiated PEO surface. While the chemical contrast in friction force had a linear dependence on the EB irradiation dose, the dependence of the chemical contrast in the phase lag was strongly non-linear. As the friction and adhesive forces depended on the AFM probe hydrophilicity and air humidity, the contrast in friction and adhesive forces is ascribed to different capillary condensation of ambient water vapour at the AFM tip contact with the EB irradiated and non-irradiated PEO surfaces, respectively.     

Nanoscale electrical properties of ZnO nanorods grown by chemical bath deposition

Well‐aligned zinc oxide nanorod arrays (ZNAs) synthesized using chemical bath deposition were fabricated on a gallium‐doped zinc oxide substrate, and the effects of varying the precursor concentrations on the growth and nanoscale electrical properties of the ZNAs were investigated. The as‐synthesized ZNAs were characterized using field‐emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), conducting atomic force microscopy (CAFM), and scanning surface potential microscopy (SSPM). The FESEM and AFM images show that the growth rate in terms of length and diameter is highly sensitive to the precursor concentration. CAFM and SSPM analyses indicate that when concentrations of both the zinc acetate and hexamethylenetetramine solutions were 30 mM, the coverage percentages of the recordable and conducting regions on the ZNA surface were 48.3% and 0.9%, which is suitable for application in resistive random access memory devices.     

Chemical force microscopy of self-assembled monolayers on sputtered gold films patterned by phase separation

Patterned self-assembled monolayers (SAMs) were formed on gold films and observed by friction force microscopy (FFM) and adhesive force mapping with pulsed-force mode atomic force microscopy (PFM-AFM). The substrate gold films were prepared by sputtering gold on flat surfaces of osmium-coated cover glass with surface roughness, Ra, of 0.3 nm. The patterned samples with the CH3 and COOH terminated regions were prepared using the Langmuir-Blodgett (LB) method, partial removal of the LB film by ultrasonication, and SAM formation. The CH3 and COOH terminated regions of the patterned SAMs in air and in water were observed by mapping friction and adhesive forces with FFM and PFM-AFM, respectively, using gold-coated AFM tips chemically modified with a thiol compound terminating in CH3 or COOH. The adhesive forces measured in air increased in the order of CH3/CH3, CH3/COOH (or COOH/CH3) and COOH/COOH, while those in water increased in reverse order. The enormous high adhesive force observed in water for CH3/CH3 was attributed to hydrophobic interaction between the CH3 tip and the CH3 terminated sample surface. With CH3 tip, the lower friction force was observed, however, in water on the CH3 terminated region than on the COOH terminated region. This experimental finding raises a question as to what is the effective normal load in friction measurements in water.     

Feedback based simultaneous correction of imaging artifacts due to geometrical and mechanical cross-talk and tip-sample stick in atomic force microscopy

This paper presents a feedback scheme that simultaneously corrects, in real time, for the imaging artifacts caused by cantilever and photosensor misalignments as well as misinterpretations in relative lateral position of the tip with respect to the sample due to the tip-sample stick in atomic force microscopy (AFM). The optical beam bounce method, typically used in AFM for imaging, is sensitive to inaccuracies of cantilever geometry and the relative misalignment of the laser source, cantilever, and the laser sensitive diode from the intended design. These inaccuracies, which contribute to the geometrical cross-talk between the normal and the lateral signals, become prominent at the atomic and subnanometer scales, and thereby impede high resolution imaging studies. The feedback scheme accounts for these artifacts and makes imaging insensitive to, in fact, practically independent of these inaccuracies. This scheme counteracts the lateral twisting dynamics of the cantilever, and as a result, it avoids the misinterpretation problem of the relative lateral position of the cantilever tip from the sample and thereby avoids the corresponding imaging artifacts that are typically prominent in contact mode friction force microscopy (FFM). The feedback scheme consists of simultaneously regulating the normal as well as the lateral cantilever deflection signal at their respective set points. This not only removes the imaging artifacts due to geometrical misalignments, mechanical cross-talk, and irregular sliding but also the corresponding compensatory control signal gives a more accurate real time measure of the lateral interaction force between the sample and the cantilever as compared to the lateral deflection signal used in FFM. Experimental results show significant improvement, and in some cases, practical elimination of the artifacts. The design and implementation of a split piezoassembly needed for the lateral actuation for the feedback scheme are also presented.     

Molecular dynamics simulation of the contact process in AFM surface observations

In the present work, several molecular dynamics simulations have been performed to clarify dynamically the contact mechanism between the specimen surface and probe tip in surface observations by an atomic force microscope (SFM) or friction force microscope (FFM). In the simulation, a three‐dimensional model is proposed where the specimen and the probe are assumed to consist of monocrystalline copper and rigid diamond or a carbon atom, respectively. The effect of the cantilever stiffness of the AFM/FFM is also taken into consideration. The surface observation process is simulated on a well‐defined Cu{100} surface. From the simulation results it has been verified that the surface images and the two‐dimensional atomic‐scale stick‐slip phenomenon, just as is the case for real AFM/FFM surface observations, can be detected from the spring force acting on the cantilever. From the evaluation of the behaviour of specimen surface atoms, the importance of the specimen stiffness in deciding the cantilever properties can also be understood. The influence of the probe tip shape on the force images is also evaluated. From the results it can be verified that the behaviour of the specimen surface atoms as well as the solid surface images in AFM/FFM surface observations can be understood using the molecular dynamics simulation of the model presented.     

Mechanical Property Investigation of Soft Materials by Cantilever‐Based Optical Interfacial Force Microscopy

Cantilever‐based optical interfacial force microscopy (COIFM) was applied to the investigation of the mechanical properties of soft materials to avoid the double‐spring effect and snap‐to‐contact problem associated with atomic force microscopy (AFM). When a force was measured as a function of distance between an oxidized silicon probe and the surface of a soft hydrocarbon film, it increases nonlinearly in the lower force region below ∼10 nN, following the Herzian model with the elastic modulus of ∼50 MPa. Above ∼10 nN, it increases linearly with a small oscillatory sawtooth pattern with amplitude 1–2 nN. The pattern suggests the possible existence of the layered structure within the film. When its internal part of the film was exposed to the probe, the force depends on the distance linearly with an adhesive force of −20 nN. This linear dependence suggests that the adhesive internal material behaved like a linear spring with a spring constant of ∼1 N/m. Constant‐force images taken in the repulsive and attractive contact regimes revealed additional features that were not observed in the images taken in the noncontact regime. At some locations, however, contrast inversions were observed between the two contact regimes while the average roughness remained constant. The result suggests that some embedded materials had spring constants different from those of the surrounding material. This study demonstrated that the COIFM is capable of imaging mechanical properties of local structures such as small impurities and domains at the nanometer scale, which is a formidable challenge with conventional AFM methods. SCANNING 35:59‐67, 2013. © 2012 Wiley Periodicals, Inc.     

Tribological Behavior of TiAlN,AlTiN, and AlCrN Coatings at Boundary Lubricating Condition

In this study, ~?3.5 µm thick multilayer titanium alumina nitride (TiAlN), alumina titanium nitride (AlTiN), and alumina chromium nitride (AlCrN) coatings were deposited on the H13 steel surface by cathodic arc physical vapor deposition (CAPVD) method. The tribological performance of the coatings was evaluated by a tribometer at boundary lubrication condition. Then, coating surfaces were observed by optical microscope, optical profilometer, and atomic force microscope to evaluate the morphological changes, wear volumes, and tribofilm thickness. Also, scanning electron microscopy (energy dispersive X-ray) and X-ray photoelectron spectrometry analyses were applied to coating surfaces for the tribochemical evolution of the tribofilm. Results showed that AlCrN coating performed the best tribological behavior at boundary lubricated condition, when compared to TiAlN and AlTiN coatings and it can be used as a wear resistant cam tappet coating in internal combustion engines.     

Mapping of enzyme activity by detection of enzymatic products during AFM imaging with integrated SECM-AFM probes

With the integration of submicro- and nanoelectrodes into atomic force microscopy (AFM) probes using microfabrication techniques, an elegant approach combining scanning electrochemical microscopy (SECM) with AFM has recently been introduced. Simultaneous contact mode imaging of a micropatterned sample with immobilized enzyme spots and imaging of enzyme activity is shown. In contrast to force spectroscopy the conversion of an enzymatic byproduct is directly detected during AFM imaging and correlated to the activity of the enzyme.     

Microstructure of Monoplacophora (Mollusca) shell examined by low-voltage field emission scanning electron and atomic force microscopy

The shell of Micropilina arntzi (Mollusca: Monoplacophora), a primitive molluscan class, was examined by using field emission scanning electron microscopy (FESEM) at low voltage and atomic force microscopy (AFM). The use of these two techniques allowed the observation of fine details of Micropilina arntzi shell and contributed to bring new features concerning the study of molluscan shell microtexture. Imaging with low-voltage FESEM provided well-defined edge contours of shell structures, while analyzing the sample with AFM gave information about the step height of stacked internal structures as well as the dimension of the particles present in their surface at a nanometric level. The shell microstructure of Monoplacophora species presents different patterns and may be a taxonomic implication in the systematic studies of the group.     

Investigation of protein partnerships using atomic force microscopy

The origin of contrast in atomic force microscopy (AFM) lies in the probe's response to forces between itself and the sample. These forces most commonly result from changes in height as the tip is scanned over the surface, but can also originate in properties inherent in the sample. These have been exploited as further means of contrast and have spawned an array of similar imaging techniques, such as chemical force microscopy, magnetic force microscopy, and frictional force microscopy. All of these techniques use AFM as an extremely sensitive gauge to map forces at discrete sites on the surface. A natural extension of this approach is to map forces in an array, in order to create a force map. AFM can be used in aqueous or fluid environments, thus allowing the exploration of forces in biological systems under physiologically relevant conditions. By immobilizing one half of an interacting pair of proteins onto the tip and the other half onto the substrate, it is possible to investigate the electrostatic and hydrophobic interactions between them. We employed these techniques to examine the interaction between a pair of proteins of known affinity that are involved in exocytosis (NSF and alpha-SNAP) and separately to demonstrate how two-dimensional force mapping can be applied to the nuclear envelope to identify nuclear pore complexes.     

Identification and ultrastructural imaging of photodynamic therapy-induced microfilaments by atomic force microscopy

Atomic force microscopy (AFM) is an emerging technique for imaging biological samples at subnanometer resolution; however, the method is not widely used for cell imaging because it is limited to analysis of surface topology. In this study, we demonstrate identification and ultrastructural imaging of microfilaments using new approaches based on AFM. Photodynamic therapy (PDT) with a new chlorin-based photosensitizer DH-II-24 induced cell shrinkage, membrane blebbing, and reorganization of cytoskeletons in bladder cancer J82 cells. We investigated cytoskeletal changes using confocal microscopy and atomic force microscopy. Extracellular filaments formed by PDT were analyzed with a tandem imaging approach based on confocal microscopy and atomic force microscopy. Ultrathin filaments that were not visible by confocal microscopy were identified as microfilaments by on-stage labeling/imaging using atomic force microscopy. Furthermore, ultrastructural imaging revealed that these microfilaments had a stranded helical structure. Thus, these new approaches were useful for ultrastructural imaging of microfilaments at the molecular level, and, moreover, they may help to overcome the current limitations of fluorescence-based microscopy and atomic force microscopy in cell imaging.     

AFM imaging in solution of protein-DNA complexes formed on DNA anchored to a gold surface

A chemical procedure for anchoring DNA molecules to gold surfaces was used to facilitate the imaging of DNA and DNA-protein complexes in buffer solution by tapping mode atomic force microscopy (TMAFM). For preparing flat gold surfaces, a novel approach was employed by evaporating small amounts of gold onto freshly cleaved mica to give flat films that were stable under aqueous buffer conditions. The thickness of the investigated films ranged from 1 to 10 nm. For typical films of 4-6 nm, which were stable under aqueous buffer conditions, the root mean square (RMS) roughness ranged between 0.25 and 0.5 nm, as measured by atomic force microscopy (AFM). This roughness is comparable to that of obtained by the template stripped gold (TSG) technique, which is widely used in scanning probe microscopy but involves more preparation steps. In order to visualize DNA and DNA-protein complexes by TMAFM, the DNA was chemisorbed to the gold surface through a linker carrying a terminal thiol group at the 5'-end of each of the DNA strands. The modified DNA fragments were bound to the gold films and imaged in buffer solution, while unmodified DNA could not be visualized. Since the DNA was not dried during the process, it can be assumed that its native conformation was retained. This mode of anchoring did not prevent interaction with proteins, as confirmed by the observation that the topology of a complex formed by adding the protein to a surface-anchored DNA was the same as that obtained by anchoring a pre-formed complex to the gold surface. We attribute this observation to the fact that the DNA is anchored to the gold surfaces only through its ends, therefore the DNA-support interaction is minimized but imaging is still possible.     

Atomic Friction Modulation on the Reconstructed Au(111) Surface

Friction between a nanoscale tip and a reconstructed Au(111) surface is investigated both by atomic force microscopy (AFM) and molecular statics calculations. Lateral force AFM images exhibit atomic lattice stick–slip behavior with a superstructure corresponding to the herringbone reconstruction pattern. However, the superstructure contrast is not primarily due to variations in the local frictional dissipation (which corresponds to the local width of the friction loop). Rather, the contrast occurs primarily because the local centerline position of the friction loop is periodically shifted from its usual value of zero. Qualitatively, similar behavior is reproduced in atomistic simulations of an AFM tip sliding on the reconstructed Au(111) substrate. In both simulations and experiments, this centerline modulation effect is not observed on unreconstructed surfaces. Similarly, using a topographically flat surface as a hypothetical control system, the simulations show that the centerline modulation is not caused by variations in the reconstructed surface’s topography. Rather, we attribute it to the long-range variation of the local average value of the tip-sample interaction potential that arises from the surface reconstruction. In other words, surface atoms located at unfavorable sites, i.e., in the transition between face-centered-cubic (FCC) and hexagonal-close-packed (HCP) regions, have a higher surface free energy. This leads to a varying conservative force which locally shifts the centerline position of the friction force. This demonstrates that stick–slip behavior in AFM can serve as a rather sensitive probe of the local energetics of surface atoms, with an attainable lateral spatial resolution of a few nanometers.     

AFM针尖"突跳"研究

为了研究原子力显微镜（AFM）“突跳”现象的产生机理，基于经典弹性理论和Lennard-Jones势能定律建立了AFM针尖与样品纳米接触的弹性模型。给出了在AFM针尖逐渐趋近样品表面的过程中，AFM针尖与样品间的粘着力、样品表面的轮廓曲线和样品表面的变形量随AFM针尖与样品表面间距的变化规律。分析了AFM“突跳”现象的产生机理和影响因素。研究表明，AFM“突跳”现象主要是由样品表面在粘着引力的作用下产生拉伸变形并与AFM针尖“突跳”接触引起的。